Color-forming carboxamidonaphthalene dye precursor compounds, photographic materials containing them and corresponding carboximide dyes

Abstract

 A new color-forming 4-(4'-secondary or tertiary-amino anilinol-1-carboxamidonaphthalene dye precursor in a silver halide photographic material enables formation of a dye image by means of cross-oxidation during development of the silver halide without the need for a coupling reaction. The exposed photographic material may be processed to produce (a) a positive dye image, (b) a negative dye and negative silver image, (c) a negative dye image or (d) a positive dye image and a positive silver image. New naphthoquinone-imide dyes corresponding to the new dye precursors are also described.

Description

[0001] The invention relates to color-forming carboxamidonaphthalene dye precursor compounds and corresponding carboximide dyes that are useful in imaging materials, such as photographic silver salt materials, and processes. The dye precursor compounds are 4-(4'-secondary or tertiary-amino - anilino)-1-carboxamidonaphthalenes.

[0002] Photographic materials for producing silver images and dye images are known. The dye image in such materials is produced by a coupling reaction in which a developing agent is oxidized upon development of photosensitive silver halide in the material, followed by reaction of the resulting oxidized form of the developing agent with a coupling agent to produce a dye image.

[0003] A method of producing reversal color images, also known as positive dye images, which involves developing a silver image in an imagewise exposed photographic material has been suggested in, for example, U.S. Patent 4,035,184 and U.S. Patent 3,938,995. These patents describe production of a dye image through oxidation, by oxidized developing agent of the leuco form of an image dye. This leuco dye is the reaction product of a color-forming coupler and a suitably substituted N,N-dialkyl-p-phenylenediamine and is incorporated in the silver halide photographic material.

[0004] It has been desirable to provide alternative means for producing a dye image, especially a dye image that enhances a silver image

[0005] The present invention provides a color-forming carboxamidonaphthalene dye precursor compound comprising a benzene ring attached by an -NH- group to a naphthalene nucleus wherein:

a) the benzene ring has a secondary or tertiary amino group in the para position relative to the -NH- group;

(b) the naphthalene nucleus has a carboxamido group in the para position relative to the -NH- group; and

(c) the benzene ring and the naphthalene nucleus are optionally further substituted; the compound being capable, on oxidation, of forming a carboximide dye.

[0006] The dye precursor compounds of the invention provide a means for producing a dye image, especially a dye image that enhances a silver image, without requiring a coupling reaction. Further, the dye produced has good stability.

[0007] The dye produced from a dye precursor compound of the invention is a carboximide dye comprising a benzene ring attached by an -N- group to a naphthalene nucleus in quinone form wherein:

(a) the benzene ring has a secondary or tertiary amino group in the para position relative to the -N- group;

(b) the naphthalene nucleus in quinone form has a carboximido group in the para position relative to the -N- group; and,

(c) the benzene ring and the naphthalene nucleus in quinone form are optionally further substituted.

[0008] The dye precursor compounds may be incorporated in photographic silver halide materials.

[0009] A stable dye image, especially a dye image that enhances a silver image, may be produced in a photographic material comprising a support having thereon, preferably in a binder: (a) photosensitive silver halide, and associated therewith (b) a color-forming dye precursor of the invention by imagewise converting the precursor to a dye upon exposure and processing of the photographic material. The dye may be formed by cross-oxidation, preferably by means of a cross-oxidizing silver halide developing agent. A combination of color-forming dye precursors may be used, if desired.

[0010] A positive dye image may be provided in a photographic material as just described by a process comprising (a) developing a silver image in the exposed photographic material using an alkaline photographic developer in the absence of a cross-oxidizing silver halide developing agent; then, (b) fogging the residual silver halide, such as by uniformly exposing the resulting material to a flash exposure of light or, alternatively, a chemical fogging agent; followed by (c) producing a dye image by developing the photographic material in an alkaline cross-oxidizing developer, such as a 3-pyrazolidone cross-oxidizing developer; and, then (d) bleaching and fixing the photographic material in a silver halide bleaching and fixing composition to produce the positive dye image. After step (a) and before
step (b), optionally the photographic process for producing a positive dye image includes a stop bath treatment. This permits a desirable lowering of the pH of the development to a point at which development of a negative silver image stops quickly. This produces an improved dye image upon processing.

[0011] A negative dye image and a negative silver image may be produced in an imagewise exposed photographic material comprising, in association, (a) photosensitive silver halide, and (b) a dye precursor of the invention by developing the photographic material in an alkaline, cross-oxidizing, photographic silver halide developer composition, preferably such a composition comprising a 3-pyrazolidone silver halide developing agent. The negative dye image preferably enhances the negative silver image. This enables a lower concentration of silver to be used in the photographic material before exposure than otherwise might be necessary to form a similar developed image from silver halide alone. When the negative, developed silver image is at least partially removed from the photographic material, such as by means of a bleaching and fixing composition, a negative dye image remains in the processed photographic material.

[0012] A positive dye image and a positive silver image may be produced in an imagewise exposed photographic material comprising, in association, (a) direct-positive photographic silver halide, and (b) a color-forming dye precursor of the invention by (A) developing the photographic material using an alkaline, cross-oxidizing photographic silver halide developing composition; then (B) fixing the resulting photographic material to produce a positive dye image and a positive silver image.

[0013] In each of the photographic materials and processes described above, the resulting naphthoquinoneimide dye in the image areas has good stability. The naphthoquinoneimide dye exhibits an increase in stability compared to a corresponding benzoquinoneimide dye. In the naphthoquinoneimide dyes, a ureido group provides increased stability compared to corresponding dyes comprising other carboxamido groups than a ureido group.

[0014] In addition to the uses described above, the dye precursor compound of the invention may be incorporated in a photographic silver halide processing composition for producing a dye-enhanced silver image wherein the composition comprises a cross-oxidizing photographic silver halide developing agent.

[0015] Preferred color-forming 4-(4'-secondary or tertiary-amino anilinop_i-carboxamidonaphthalene dye precursors of the invention are represented by the formula:

wherein,

R¹ is alkyl, such as alkyl containing 1 to 25 carbon atoms, for example methyl, ethyl, propyl, butyl, decyl and eicosyl; cycloalkyl containing 5 to 8 carbon atoms, for example cyclohexyl and cyclopentyl; aryl, such as aryl containing 6 to 25 carbon atoms, for example, phenyl, tolyl and xylyl; alkoxy, such as alkoxy containing 1 to 25 carbon atoms, for example, methoxy, ethoxy, butoxy and decyloxy; aryloxy, such as aryloxy containing 6 to 25 carbon atoms, for example, phenoxy, tertiary-butylphenoxy and di-tertiary-amylphenoxy;

or a 5 or 6 member heterocyclic group, for example a 5 or 6 member heterocyclic group comprising atoms selected from nitrogen, oxygen, sulfur, carbon and hydrogen atoms, for example, morpholino, pyrrolino, pyridino, pyrimidino, oxazolino, thiazolino, and thiopheno;

R², R³ , R⁴ , R⁵ , R⁶ andR7 are individually hydrogen; alkyl, such as alkyl containing 1 to 25 carbon atoms, for example, methyl, ethyl, propyl, butyl, decyl and eicosyl; aryl, such as aryl containing 6 to 25 carbon atoms, for example, phenyl, tolyl and xylyl; alkoxy, such as alkoxy containing 1 to 25 carbon atoms, for example, methoxy, ethoxy, butoxy and decyloxy; arylsulfonyl (Ar-S0₂-), such as arylsulfonyl containing 6 to 25 carbon atoms, for example, phenylsulfonyl, naphthylsulfonyl, xylylsulfonyl and tolylsulfonyl; chlorine; bromine; carbamoyl; sulfamoyl; carboxy; sulfonamido; and carboxamido;

R^e is hydrogen; alkyl, such as alkyl containing 1 to 25 carbon atoms, for example, methyl, ethyl, propyl, butyl, decyl, eicosyl, hydroxyethyl, methylsulfonamidoethyl and tolylsulfonamidopropyl; aryl, such as aryl containing 6 to 25 carbon atoms, for example phenyl, tolyl and xylyl; acyl, such as acyl containing 2 to 25 carbon atoms, for example acetyl, ethanoyl, heptanoyl, pivaloyl, undecanoyl, benzoyl and methylbenzoyl; carbamoyl, such as carbamoyl containing 2 to 25 carbon atoms, for example methylcarbamoyl, ethylcarbamoyl, decylcarbamoyl, and phenylcarbamoyl;

R⁹ is alkyl, such as alkyl containing 1 to 25 carbon atoms, for example methyl, ethyl, propyl, butyl, decyl, eicosyl, hydroxyethyl, methylsulfonamidoethyl, tolylsulfonamidopropyl; aryl, such as aryl containing 6 to 25 carbon atoms, for example phenyl, tolyl and xylyl; acyl containing 2 to 25 carbon atoms, such as alkylcarbonyl containing 2 to 25 carbon atoms, for example acetyl, ethanoyl, heptanoyl, pivaloyl and undecanoyl, or such as arylcarbonyl containing 7 to 25 carbon atoms, for example benzoyl and methylbenzoyl; carbamoyl, such as carbamoyl containing 2 to 25 carbon atoms, for example methylcarbamoyl, ethylcarbamoyl, decylcarbamoyl and phenylcarbamoyl;

R¹⁰ and R¹¹ are individually hydrogen; alkyl, such as alkyl containing 1 to 25 carbon atoms, for example, methyl, ethyl, propyl, butyl, decyl and eicosyl; aryl, such as aryl containing 6 to 25 carbon atoms, for example phenyl, tolyl and xylyl; an aliphatic carbocyclic group, such as a 5 or 6 member carbocyclic group, for example, cyclohexyl, said carbocyclic group optionally containing a total of 6 to 8 carbon atoms; or, taken together represent the atoms, such as the oxygen, nitrogen, sulfur, carbon and hydrogen atoms, necessary to complete a 5 or 6 member heterocyclic ring, such as pyrrolino, pyridino, pyrimidino, thiazolino and oxazolino; and

R¹², R¹³ , R¹⁴ and R¹⁵ are individually substituents that do not adversely affect desired photographic properties, for instance, hydrogen; alkyl, such as alkyl containing 1 to 25 carbon atoms, for example, methyl, ethyl, propyl, butyl, decyl and eicosyl; cyano (-CN); carboxamido; sulfonamido; sulfamoyl; chlorine; bromine; and alkoxy, such as alkoxy containing 1 to 25 carbon atoms, for example, methoxy, ethoxy, propoxy and eicosyloxy; all alkyl and aryl groups, when present as such or as part of another substituent, being optionally substituted. by groups which do not adversely affect the dye precursors or the corresponding dyes.

[0016] Examples of suitable substituted alkyl groups include alkyl containing a sulfonamido group, such as CH₃SOzNH-, a carboxamido group, an alkoxy group, such as methoxy or ethoxy, hydroxy, carboxyl (-COOH), an aryl group, alkylcarbonyl, such as methylcarbonyl and ethylcarbonyl, arylcarbonyl, such as phenylcarbonyl, alkylamino, such as methylamino and ethylamino, and arylamino, such as phenylamino. Another example of a substituted alkyl group is

[0017] An alkyl group containing an aryl substituent is also known as an aralkyl group e.g. a benzyl group. Examples of suitable substituted aryl groups include phenyl containing an alkoxy group, such as methoxy and ethoxy, carboxyl, alkyl such as methyl, ethyl, propyl and butyl, and hydroxy. An especially useful substituted aryl group is an alkyl substituted aryl group, such as tolyl, 2,4,6-triisopropylphenyl and t-butylphenyl. An alkyl substituted aryl group is also known as an alkaryl group.

[0018] Particularly preferred dye precursors are those wherein R¹ is NH-R¹⁰. A ureido group is provided on the naphthalene nucleus which enhances dye stability and increases the ease of dye formation.

[0019] An example of a preferred class of color-forming compounds according to the invention is represented by the formula:

wherein,

R¹⁶ is alkyl containing 1 to 25 carbon atoms, cycloalkyl containing 5 to 8 carbon atoms; aryl containing 6 to 25 carbon atoms; alkoxy containing 1 to 25 carbon atoms; aryloxy containing 6 to 25 carbon atoms; or

R¹⁷ is hydrogen, alkyl containing 1 to 25 carbon atoms or acyl containing 2 to 25 carbon atoms;

R¹⁸ is alkyl containing 1 to 25 carbon atoms or acyl containing 2 to 25 carbon atoms;

R¹⁹ is hydrogen or alkyl containing 1 to 25 carbon atoms;

R²⁰ is hydrogen, carboxamido or alkyl containing 1 to 25 carbon atoms; and,

_R²¹ and _R²² are individually hydrogen, alkyl containing 1 to 25 carbon atoms, aryl containing 6 to 25 carbon atoms or together are the atoms selected from carbon, hydrogen, nitrogen and oxygen atoms necessary to complete a 5 or 6 member heterocyclic group, such as morpholino, piperizino and pyrrolidino.

[0020] Examples of useful color-forming dye precursors according to the invention include:

[0021] An especially preferred color-forming compound of this invention for use in a photographic material comprising a support having thereon, in association, in a gelatino binder: (a) photosensitive silver halide; and (b) a color-forming compound which is imagewise converted upon exposure and processing of thematerial to a dye by cross-oxidation by means of a cross-oxidizing developing agent, is represented by the formula:

[0022] As used herein, a carboxamido group means a group represented by the formula:

wherein R²³ is a substituent which does not adversely affect the color-forming dye precursor or imide dye. R is, for example, alkyl containing 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, decyl, and eicosyl, or aryl containing 6 to 20 carbon atoms, such as phenyl and tolyl. Examples of such groups include phenylcarboxamido, methylcarboxamido and tolylcarboxamido.

[0023] As used herein, a sulfonamido group means an unsubstituted sulfonamido group or a sulfonamido group that is substituted by a group that does not adversely affect the desired properties of the color-forming dye precursor. A sulfonamido group may be, for example, a group represented by the structure:

wherein,

Z is a substituent, such as alkyl containing 1 to 25 carbon atoms, for example methyl, ethyl, propyl, butyl, decyl and eicosyl, or aryl containing 6 to 25 carbon atoms, such as phenyl, tolyl and naphthyl. Examples of sulfonamido groups include methylsulfonamido, tolylsulfonamido, 2,4,6-triethylphenylsulfonamido, and 2,4,6-triisopropylsulfonamido.

[0024] As used herein, a carbamoyl group means an unsubstituted carbamoyl group or a carbamoyl group that is substituted by a group that does not adversely affect the desired properties of the color-forming dye precursor. A carbamoyl group herein means, for example, a group represented by the structure:

wherein,

[0025] R²⁴ is a substituent, such as alkyl containing 1 to 25 carbon atoms, for example methyl, ethyl, propyl, butyl, decyl and eicosyl, or aryl containing 6 to 25 carbon atoms, such as phenyl, tolyl and naphthyl.

[0026] Examples of carbamoyl groups include methylcarbamoyl, ethylcarbamoyl, and phenylcarbamoyl.

[0027] As used herein, a sulfamoyl group means an unsubstituted sulfamoyl group or a sulfamoyl group that is substituted by a group that does not adversely affect the desired properties of the color-forming dye precursor. A sulfamoyl group herein means, for example, a group represented by the structure:

wherein,

R^28a and R^24b are individually hydrogen or a substituent, such as alkyl containing 1 to 25 carbon atoms, for example methyl, ethyl, propyl, butyl, decyl and eicosyl, or aryl containing 6 to 25 carbon atoms, such as phenyl, tolyl and xylyl.

[0028] Examples of sulfamoyl groups include: -SOzNH₂, -SOzNHCHs, -S0₂ NHCH₂ CH₃ ,

[0029] The color-forming dye precursors are prepared by condensation of a phenylenediamine compound with a substituted halonitronaphthalene wherein the nitro group is in the 4 position with respect to a halogen atom on the naphthalene ring, followed by reduction of the nitro group and subsequent formation of the amidonaphthalene from the intermediate amine.

[0030] An illustrative method of preparation of a color-forming dye precursor according to the invention is the preparation of 4 {-4-[N-(2-methylsulfonamidoethyl)ethylamino]-2-methylanilino]-1-(N'-octylureido)-naphthalene as follows:

4-[N-(2-methylsulfonamidoethyl)ethylamino]-2-methylaniline (54.2 g, 0.2 mol) and 4-fluoro-l-nitronaphthalene (32.2 g, 0.2 mol) were stirred at 85°C under nitrogen with pyridine (31.6 g, 0.4 mol) in dimethylsulfoxide (500 ml) for 24 hours. The resulting mixture is then poured into ice water and extracted with a suitable solvent, such as methylene chloride. The extract is washed with water, dried and concentrated. The resulting intermediate product is purified, such as by crystallization from ethanol to produce a purified intermediate (m.p. 170-172°C). The resulting intermediate is reduced in dry tetrahydrofuran containing a catalytic amount

of palladium on charcoal at 276 kPa (40 psi) hydrogen pressure in a Parr apparatus. After removal of the catalyst, such as by filtration, octyl isocyanate is added to the filtrate. The mixture is stirred for 16 hours, water (100 ml) is added and the product is taken up in ether. The resulting solution is dried, filtered and concentrated. The resulting product is purified, such as by recrystallization from methanol. The purified compound has a melting point of 132-133°C.

[0031] Another example of a preparation according to the invention is the preparation of 4-(4'-N,N-diethylamino-2-methylanilino)-1-decanamidonaphthalene. This preparation is as follows:

4-(4-N,N-diethylamino-2-methylanilino)-l-nitronaphthalene (12 g., 0.0034 mole) is reduced in tetrahydrofuran (200 ml) on a Parr apparatus by means of a catalyst, such as palladium on charcoal, at 276 kPa (40 pounds per square inch) hydrogen pressure. The catalyst is then removed. Acid acceptor, such as triethylamine (11.2 ml, 0.08 mole) is added. Then decanoyl chloride (12.7 g., 0.0037 mole) in tetrahydrofuran (50 ml) is added drop-wise. The resulting mixture is stirred until reaction completion, such as for about lb hours. Water is added and the product taken up with a solvent, such as ether. Following drying and concentration of the solvent solution, the residue is typically purified, such as by recrystallization from ethanol and then methanol, to produce a white crystalline product having a melting point of 147 to 148°C.

[0032] The color-forming 4-(4'-secondary or tertiary-amino anilino)-l-carboxamidonaphthalene dye precursors may be used in a photographic material and process in a range of concentrations. Selection of an optimum concentration of the dye precursor or combination of such dye precursors depends upon the desired image, the particular photographic material, processing steps and conditions, other components in the photographic material, and the particular dye precursor. A preferred concentration of dye precursor is within the range of 0.1 to 0.6 mole of per mole of photosensitive silver halide in the photographic material. An especially useful concentration of color-forming dye precursor is within the range of 0.1 to 0.2 mole per mole of silver halide in the photographic material. In a photographic material, a preferred concentration of color-forming dye precursor is within the range of 0.5 to 22 mg per square decimeter of support, such as a concentration within the range of 5 to 11 mg per square decimeter of support.

[0033] The hue of the dye produced from the color-forming dye precursor will vary, depending upon such factors as the particular groups on the color-forming dye precursor, processing conditions, other components in the photographic material such as dispersion solvents, and whether a combination of dyes is present in the photographic material or not. The color-forming dye precursor in the photographic material is preferably colorless prior to exposure and processing. Some of the suitable color-forming dye precursors have a slight color, such as a slight yellow color, in the photographic material. This slight color is not considered unacceptable.

[0034] The color-forming dye precursor generally absorbs electromagnetic radiation outside the visible region of the electromagnetic spectrum before imagewise exposure and processing of the photographic material. The nature of the absorption and degree of absorption of the color-forming dye precursor depends upon the nature, for the most part, of the substituent groups on the color-forming dye precursor.

[0035] The photographic materials may comprise a photosensitive component which consists essentially of photographic silver halide. Examples of useful photographic silver halides are silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide, silver iodide and mixtures thereof. The silver halide may be present in the photographic material in the form of an emulsion which is a dispersion of the photographic silver halide in a suitable binder. The silver halide may be present in a range of grain sizes from fine grain to coarse grain. Negative and direct positive silver halide emulsions may be used. Such photographic emulsions are described in, for example, Research Disclosure, December, 1978, Item No. 17643. A composition containing the silver halide may be prepared by any of the well known procedures in the photographic art, such as described in Research Disclosure, December 1978, Item No. 17643.

[0036] The photographic material may contain addenda commonly found to be useful in silver halide photographic materials. These addenda include chemical sensitizers, brighteners, antifoggants, emulsion stabilizers, light absorbing and scattering materials, hardeners, coating aids, plasticizers, lubricants, antistatic materials, matting agents, and development modifiers, as described in Research Disclosure, December 1978, Item No. 17643.

[0037] The photographic silver halide may be spectrally sensitized by means of spectral sensitizing dyes, as described in, for example, Research Disclosure, December 1978, Item No. 17643. Useful spectral sensitizing dyes include such dyes as polymethine dyes which include the cyanines, merocyanines, complex cyanines and merocyanines (including tri, tetra and polynuclear cyanines and merocyanines), as well as oxonols, hemioxonols, styryls, merostyryls and streptocyanines. Combinations of spectral sensitizing dyes may be used.

[0038] The photographic silver halide may be used in a range of concentrations in a photographic material. An optimum concentration of photographic silver halide depends upon such factors as the desired image, processing conditions, particular dye precursor, other components of the photographic material and the particular photographic silver halide. A preferred concentration of photographic silver halide is within the range of 2 to 7 moles of per mole of color-forming dye precursor in the photographic material. The coverage of photographic silver halide is less than otherwise might be required, due to the enhancing properties of the dye produced upon processing of the photographic material.

[0039] The color-forming dye precursor may be in any location in a silver halide photographic material which allows production of the desired dye upon processing. Thus, the color-forming dye precursor may, if desired, be in a layer adjacent or contiguous to the layer comprising the photosensitive silver halide.

[0040] The color-forming dye precursor is frequently Lmmobilized in an oil phase in the photographic material. This enables the dye precursor to be dispersed satisfactorily. Alternatively, the color-forming dye precursor is dispersed in a dispersion solvent to produce a desired photographic material. Coupler solvents known in the photographic art are useful for aiding dispersion of the color-forming dye precursor. Examples of useful coupler solvents include N-n-butylacetanilide, diethyl lauramide, di-n-butyl phthalate and 2,4-ditertiaryamylphenol. The color-forming dye precursor may also be loaded into a latex or a nonsolvent dispersion may be prepared, if desired.

[0041] Many developing agents are useful for developing an image in the photographic material. Any silver halide developing agent is may be used, provided it comprises a cross-oxidizing developing agent which will cross-oxidize with the color-forming dye precursor. Such a silver halide developer, called herein a cross-oxidizing developing agent, becomes oxidized during development by reducing exposed silver halide to silver metal. The oxidized developer then cross-oxidizes the color-forming dye precursor to form the desired dye.

[0042] A cross-oxidizing developing agent (COD) enables the color-forming dye precursor to become oxidized without the color-forming dye precursor itself developing silver. The cross-oxidizing developing agent is viewed alternatively as an electron transfer agent which shuttles electrons between the developing silver halide and the color-forming dye precursor.

[0043] The requirements for a cross-oxidizing developing agent are: (a) the developing agent must have sufficient, electrochemical potential under the conditions of use to develop exposed silver halide, (b) in its oxidized form, the developing agent must be of such electrochemical potential as to oxidize the color-forming dye precursor, and (c) in its oxidized form, the developing agent must be stable to decomposition by other chemical reactions for a sufficient period to undergo the redox reaction with the color-forming dye precursor. Whether a developing agent is a cross-oxidizing developing agent or not depends upon whether the oxidized form is sufficiently stable and the oxidizing potential is such that an effective transferral of electrons occurs through whatever phase barriers exist during cross-oxidizing development. Whether a particular developing agent meets these requirements depends upon the conditions under which development occurs. Other factors influence whether a particular developing agent is a cross-oxidizing developer, including the pH of the developing composition, the temperature of the development process and the length of development time. Examples of developing agents which are useful as cross-oxidizing developing agents include 3-pyrazolidone developers, such as l-phenyl-3-pyrazolidone, l-phenyl-4,4-dimethyl-3-pyrazolidone and 4-hydroxymethyl-4-methyl-l-phenyl-3-pyrazolidone. Such cross-oxidizing developing agents are described in, for example, U.S. Patent 3,938,995. Combinations of non-cross-oxidizing developing agents and cross-oxidizing developing agents are useful, provided a minor proportion of the non-cross-oxidizing developing agent is present, such as less than about 10 percent of the total combination is non-cross-oxidizing developing agent. Examples of combinations of a non-cross-oxidizing developing agent and a cross-oxidizing developing agent include 4-hydroxymethyl-4-methyl-l-phenyl-3-pyrazolidone with a minor proportion of at least one of the following non-cross-oxidizing developing agents:ascorbic acid, hydroquinone and pyrimidine. Selection of an optimum cross-oxidizing silver halide developing agent or developing agent combination will depend upon such factors as the desired image, the particular photosensitive silver halide, processing conditions, and the particular color-forming dye precursor.

[0044] A silver halide developing agent or silver halide developing agent combination may be incorporated in the photographic material. Generally, the silver halide developing agent is most useful in a processing solution in which the photographic material is processed after exposure.

[0045] The developing agent may be used in a range of concentration in the photographic material or in a processing composition in which the photographic material is processed. A preferred concentration of developing agent in the photographic material is within the range of 0.01 to 1.0 mole of developing agent per mole of color-forming dye precursor in the photographic material. A preferred concentration of developing agent in a processing solution for processing a photographic material containing a color-forming dye precursor is within the range of 0.5 to 2 grams of developing agent per liter of processing solution.

[0046] The term "developing agent" herein includes compounds which are developing agents or developing agent precursors. That is, those compounds are included which are not developing agents in the photographic material until a condition occurs, such as contact with a suitable activator for the photographic material.

[0047] The tone of the silver image and dye image produced in the photographic material will vary, depending upon such factors as the silver morphology of the developed silver image, the covering power of the silver materials, the particular dye formed, the particular developing agent, processing conditions, and other components in the photographic material. In photographic materials that provide a brown silver image, a dye produced is preferably complementary in hue to the silver image. A combination of dyes and a silver image that produce a neutral-appearing image are preferred.

[0048] The photographic materials may comprise a variety of binders alone or in combination. The binders include both naturally occurring substances, such as proteins, for example, gelatin, gelatin derivatives, cellulose derivatives, polysaccharides, such as dextran, and gum arabic; but also include synthetic polymeric materials, such as water-soluble polyvinyl compounds, e.g. poly(vinylpyrrolidone) and acrylamide polymers. Examples of useful binders include those described in, for instance, Research Disclosure, December 1978, Item No. 17643.

[0049] The photographic materials may contain an overcoat layer, and/or interlayer, and/or subbing layer to provide desired properties. The overcoat layer, for example, increases resistance to abrasion and other markings on the material. The overcoat layer, interlayer or subbing layer contain, alone or in combination, the described binders.

[0050] A photographic material may comprise a variety of supports. Useful supports include those that are resistant to adverse changes in structure due to processing conditions and which do not adversely affect the desired sensitometric properties of the photographic materials. Examples of useful supports include cellulose ester, poly(vinylacetal), poly(ethylene terephthalate) and polycarbonate films, as well as related films and resinous materials. Glass, paper and metal supports are also useful. A flexible support is preferred.

[0051] The photographic coating compositions may be coated on a support by procedures known in the photographic art. Such procedures include, for example, immersion or dip coating, roller coating, reversal roll coating, airknife coating, doctor blade coating, spray coating, extrusion coating, bead coating, stretch flow coating and curtain coating.

[0052] The photographic materialsmay be imagewise exposed by means of various forms of energy to produce a developable image. Such forms of energy include those to which the photosensitive silver halide is sensitive, and encompass ultraviolet, visible and infrared regione of the electromagnetic spectrum, as well as electron beam and beta radiation, gamma ray, X-ray, alpha particle, neutron radiation and other forms of corpuscular wave-like radiant energy in either coherent or non-coherent forms. Lasers may used, for example. Exposures are monochromatic orthochromatic or panchromatic depending on the spectral sensitization of the photosensitive silver halide. Imagewise exposure is generally for a sufficient time and intensity to produce a developah latent image in the photographic material.

[0053] A photographic material containing a dye precursor according to the invention may be processe in (a) a process which produces a positive dye image (b) a process which produces a negative dye image an negative silver image, (c) a process which produces negative



material is processed following exposure to form a visible image. This is done, for example, by associating the silver halide at one stage of the process with an aqueous alkaline medium in the presence of a cross-oxidizing developing agent contained in the medium and/or in the photographic material.

[0054] To produce a positive dye image, also known as a reversal dye image, it is desirable to process the exposed photographic material by means of a non-cross-oxidizing developing composition as a first development step. During this step, the exposed silver halide is reduced to elemental silver by the non-cross-oxidizing developing composition. The non-cross-oxidizing developing composition does not, when oxidized, oxidize the color-forming dye precursor according to the invention to its corresponding dye.

[0055] The non-cross-oxidizing developer composition useful in this step may be an alkaline solution, preferably an aqueous solution comprising a non-cross-oxidizing developing agent. Non-cross-oxidizing developing agents are known in the photographic art and include many silver halide developing agents which will reduce exposed photosensitive silver halide to silver, but will not oxidize the color-forming dye precursor to a corresponding dye. Examples of useful non-cross-oxidizing developing agents are described in, for example, Research Disclosure, December 1978, Item No. 17643. Useful non-cross-oxidizing developers include developer compositions comprising ascorbic acid, hydroquinone, pyrimidine developing agents and a combination of hydroquinone and N-methyl-p-aminophenol.

[0056] In a second step of the process for forming a positive dye image, fogging of the photographic material is accomplished by exposing the photographic material to light or by chewical fogging by means of chemical fogging agents known in the photographic art.

[0057] Following the described fogging step, a second silver halide developing step is carried out. This is carried out by means of a cross-oxidizing developing composition. It is in this step that the color-forming dye precursor is converted to a dye in the image areas. Any silver halide developing composition is useful in this step, provided that it cross-oxidizes the color-forming dye precursor to a desired dye. Such silver halide developing compositions include alkaline solutions comprising a cross-oxidizing silver halide developing agent, preferably a 3-pyrazolidone cross-oxidizing silver halide developing agent. This cross-oxidizing developing agent becomes oxidized during development by reducing exposed or fogged silver halide to silver metal. The oxidized developing agent then cross-oxidizes the color-forming dye precursor to a desired dye. The photographic material, upon processing, contains a concentration of dye in inverse proportion to the amount of exposure of the photographic material. That is, a positive dye image, also described herein as a reversal dye image, is formed.

[0058] An especially useful process for producing a positive dye image in an imagewise exposed photographic material containing a dye precursor of the invention comprises: (a) developing the exposed photographic material in an alkaline photographic developer in the absence of a cross-oxidizing silver halide developing agent, and then (b) uniformly exposing the material to a flash exposure of light, followed by (c) developing the photographic material in an alkaline, cross-oxidizing developer, comprising an aqueous, alkaline solution of 4-methyl-4-hydroxymethyl-l-phenyl-3-pyrazolidone, and (d) bleaching and fixing the photographic material in a silver halide bleaching and fixing solution to produce a positive dye image. It may be preferred to treat the photographic material by means of a development stop bath after step (a) and before step (b).

[0059] Photographic materials containing a dye precursor according to the invention are also useful for producing negative dye images. Such negative dye images may be produced in an exposed photographic element comprising a support having thereon, in reactive association, in a binder, (a) photosensitive silver halide, and (b) a color-forming 4-(4'-secondary or tertiary-aminoanilino)-1-carboxamidonaphthalene dye precursor by (A) developing the photographic element in an alkaline, cross-oxidizing photographic silver halide developer composition to produce a negative dye image and silver image; then (B) removing at least part of the silver image from the photographic material, such as by bleaching and fixing the silver from the material. Removal of the silver is accomplished by means of bleaching and fixing compositions known in the photographic art. The optimum bleaching and fixing compositions are selected to provide the desired dye image. Suitable bleaching and fixing compositions are described in Grant Haist. Modern Photographic Processing, Vol. 2, Chapter 10 (1979). The bleaching agent employed should be of such strength that it does not oxidize the color-forming dye precursor and thereby lead to uniform dye density in the material.

[0060] Photographic materials containing a dye precursor according to the invention comprising

images. A process of producing a positive dye image and a positive silver image in an imagewise exposed- photographic material comprising a support having thereon, in reactive association, in a binder, (a) direct-positive photographic silver halide, and (b) a color-forming 4-(4'-secondary or tertiary-amino anilino)-l-carboxamidonaphthalene dye precursor, comprises (A) developing the photographic element in an alkaline, cross-oxidizing photographic silver halide developing composition; then (B) fixing the resulting photographic material to produce a positive dye image and a positive silver image. Useful direct-positive silver halide is described in, for example, Research Disclosure, December 1978, Item No. 17643, pages 22 through 31. Fixing the photographic material is accomplished by means of fixing compositions known in the photographic art, such as a sodium thiosulfate fixing composition.

[0061] An advantage of the photographic material and process is that the dye images produced upon processing possess desired stability to post-processing conditions and visible light exposure. A simple test is useful for establishing the degree of stability which is desired for a dye image produced from a color-forming dye precursor according to the invention. One such test is a test well known in the photographic art in which a processed photographic material is exposed to a Simulated Average North American Skylight (SANS) with continuous 5400 LUX of exposure at an average temperature of 21°C at 45 percent relative humidity. A comparison of the stability of the tested dye is then observed.

[0062] When a cross-oxidizing silver halide developing agent is present in the photographic material, a developed image is produced after imagewise exposure of the photographic material by contacting the material with an alkaline activator solution which enables development of the exposed silver halide, as well as production of the desired dye. Many alkaline activators are useful for developing an image in a photographic material comprising an incorporated cross-oxidizing silver halide developing agent. Alkaline activators which are known to be useful in the photographic art, such as in stabilization processing, are useful for developing an image in the described photographic material. Examples of useful alkaline activators include sodium hydroxide, potassium hydroxide, trisodium phosphate . 12H20 (pH 12), sodium metaborate (pH 12), disodium phosphate and monosodium phosphate. An optimum alkaline activator will depend upon such factors as the desired image, the particular cross-oxidizing developing agent, processing conditions and the particular color-forming dye precursor. An especially useful alkaline activator comprises trisodium phosphate (pH 12).

[0063] The alkaline activator may be used in a range of concentrations. A preferred concentration of alkaline activator is within the range of 10 to 50 grams per liter of activator solution which produces a pH within the range of 11 to 12. An optimum concentration of alkaline activator will depend upon such factors as the desired image, the particular activator, processing conditions, particular cross-oxidizing developing agent, particular photosensitive silver halide and particular color-forming dye precursor.

[0064] After exposure and processing, the photographic material comprises a dye image or, alternatively, a dye image and a silver image. Preferred dyes are represented by the formula:

wherein, R¹ , R² , R³ , R⁴ , R⁵ , R⁶ , R , R⁸ , R⁹, R¹⁰ , R¹¹, R¹²,R¹³,R¹⁴ and R¹⁵ are as defined.

[0065] Examples of naphthoquinoneimide dyes produced from the dye precursors of the invention are:

[0066] The naphthoquinoneimide dyes have increased stability to hydrolysis compared to corresponding benzoquinoneimide dyes. This is believed to be due at least in part to the resistance which naphthoquinoneimide dyes exhibit to formation of a resonance structure that favors formation of an indoaniline dye.

[0067] The following examples are included for a further understanding of the invention.

Example 1 Preparation of 4-{4'-(N-(2-methylsulfonamidoethyl)etaylamino]-2-methyl- anilino}-1-(N'-octylureido)-naphthalene:

[0068] 

[0069] A solution of 4-[N-(2-methylsulfonamidoethyl)ethylamino]-2-methylaniline (54.2 g, 0.2 mol) and 4-fluoro-l-nitronaphthalene (32.2 g, 0.2 mol) with pyridine (31.6 g, 0.4 mol) in dimethylsulfoxide (500 ml) was stirred and heated under a nitrogen atmosphere at 85°C for 24 hours. The reaction mixture was then poured into ice water and extracted with methylene chloride. The extract was washed three times with water, dried, and concentrated. After crystallization from ethanol, an intermediate product (30.4 g, 34% yield, m.p. 171-173°C) was characterized by nuclear magnetic resonance, mass spectral and elemental analysis.

[0070] A sample of the resulting intermediate (6.0 g, 0.014 mol) was reduced in dry tetrahydrofuran (150 ml) containing a catalytic amount of palladium on charcoal at 276 kPa (40 psi) hydrogen pressure in a Parr Apparatus. After removal of the catalyst by filtration, octyl isocyanate (2.1 g, 0.014 mol) was added to the filtrate. The mixture was stirred for 16 hours, then water (100 ml) was added and the product was taken up in ether. The ethereal solution was dried, filtered and concentrated. The residue was recrystallized twice from methanol. The crystalline product (4.7 g, 59% yield, m.p. 132-133°C) was characterized by nuclear magnetic resonance and elemental analysis.

Example 2 Preparation of 4-(4'-N,N-diethyl- amino-2-methylanilino)-I-de- canamidonaphthalene:

[0071] 

4-(4-N,N-diethylamino-2-methylphenyl-amino)-1-nitronaphthalene (5.0 g, 0.014 mol) was reduced in tetrahydrofuran (200 ml) in a Parr Apparatus using palladium on charcoal catalyst at 276 kPa (40 psi) hydrogen pressure. After removal of the catalyst by filtration, first triethylamine (3 g, 0.03 mol) was added and then decanoyl chloride (3.0 g, 0.016 mol) in tetrahydrofuran (50 ml) was added drop-wise. The mixture was stirred for 16 hours. Then water (150 ml) was added and the product taken up with ether. Following drying (by means of Na₂SO₄), filtration and concentration of the ether solution, the residue was recrystallized from ethanol and then methanol. The resulting white crystalline product (2.4 g, 36% yield, m.p. 147-148°C) was characterized by nuclear magnetic resonance, mass spectral and elemental analysis.

Examples 3-7 Use in Photographic Material

[0072] In each of the following examples a photographic material was prepared by coating the following photographic composition on a subbed poly(ethyleneterephthalate) film support:

1) silver bromoiodide (0.8 micron grain, sulfur and gold chemically sensitized) (9.7 mg/dm²)

2) color-forming dye precursor as coupler solvent dispersion (1:1 to 1:2 parts by volume) (3.0 to 16.2 mg/dm²) (coverage of dispersion was adjusted to give an approximate silver plus dye density of 2.0)

3) photographic gelatin (binder) (43.2 mg/dm²), hardened by bis(vinylsulfonylmethyl)ether ((CH₂=CHSU₂CH₂)₂O) (2.0 parts by weight in 200 parts water, 0.43 mg/dm²).

[0073] Each photographic material was chemically oxidized at 22°C in the following processing sequence:

1) 30 second fix in the following fixing composition:

2) 60 second water wash

3) 30 second oxidizing treatment in the following oxidizing composition:

4) 5 minute water wash

5) 10 second water wash (in Kodak Photo-Flo Solution, which is a trademark of and available from Eastman Kodak Company, U.S.A.)

6) dry in air at room temperature (about 21°C). The resulting dried photographic materials were then exposed (emulsion side to the light) tc 5400 LUX irradiation (Simulated Average North American Skylight irradiation) for 1, 3 and 7 days. Density was measured at the maximum absorption wavelength for each dye. The percentage of dye fade was calculated based on the following formula:

wherein D equals density. Results of these examples are summarized in following Table I:

Examples 8-10

[0074] The dyes listed in following Table II were prepared by procedures similar to those described:

Examples 11 - 16

[0075] In each of the following Examples a photographic material was prepared as described in Examples 3-7. The photographic material in each case was imagewise exposed to light to produce a developable latent image in the photographic material. The exposed material was then processed at 22°C in the following processing sequence:

1) 30-second development by immersion in the following composition:

2) 2-minute water wash

3) 30-second fix in the fixing composition described in step 1 of Example 3

4) 2-minute water wash

5) dry in air at room temperature (about 21°C). The resulting dried photographic materials were then exposed (emulsion side to the light) to 5400 LUX irradiation (Simulated Average North American Skylight irradiation) for 1, 3 and 7 days. Density was measured at the maximum absorption wavelength for each dye. The percentage of dye fade was calculated as described in Example 3. A dye image and silver image was produced in each example. Results of the percentage of dye fade are summarized in following Table III:

[0076] The following compounds were prepared by procedures similar to those described in Examples 1 and 2:

Claims

1. A color-forming carboxamidonaphthalene dye precursor compound comprising a benzene ring attached by an -NH- group to a naphthalene nucleus wherein:

(a) the benzene ring has a secondary or tertiary amino group in the para position relative to the -NH- group;

(b) the naphthalene nucleus has a carboxamido group in the para position relative to the -NH- group; and

(c) the benzene ring and the naphthalene nucleus are optionally further substituted;

the compound being capable, on oxidation of forming a carboximide dye.

2. A color-forming compound according to Claim 1 represented by the formula:

wherein:

R¹ is alkyl containing 1 to 25 carbon atoms, cycloalkyl containing 5 to 8 carbon atoms, aryl containing 6 to 25 carbon atoms, alkoxy containing 1 to 25 carbon atoms, aryloxy containing 6 to 25 carbon atoms, amino of formula:

or a 5 or 6 member heterocyclic group;

R², R³ , R⁴ , R⁵, R⁶ , and R⁷ are individually hydrogen, alkyl containing 1 to 25 carbon atoms, aryl containing 6 to 25 carbon atoms, alkoxy containing 1 to 25 carbon atoms, arylsulfonyl containing 6 to 25 carbon atoms, chlorine, bromine, carbamoyl, sulfamoyl, carboxy, sulfonamido; and carboxamido;

R⁸ is hydrogen, alkyl containing 1 to 25 carbon atoms, aryl containing 6 to 25 carbon atoms, acyl containing 2 to 25 carbon atoms, or carbamoyl containing 2 to 25 carbon atoms;

R⁹ is alkyl containing 1 to 25 carbon atoms, aryl containing 6 to 25 carbon atoms, acyl containing 2 to 25 carbon atoms, or carbamoyl;

R¹⁰ and R¹¹ are individually hydrogen, alkyl containing 1 to 25 carbon atoms, aryl containing 6 to 25 carbon atoms, a carbocyclic group, or taken together represent the atoms necessary to complete a 5 or 6 member heterocyclic ring;

R¹² , R¹³ , R¹⁴ , and R¹⁵ are individually hydrogen, alkyl containing 1 to 25 carbon atoms, cyano, sulfamoyl, chlorine, carboxamido, sulfonamido, bromine and alkoxy containing 1 to 25 carbon atoms;

all alkyl and aryl groups, when present as such or as part of another substituent, being optionally substituted.

3. A color-forming compound according to Claim 1 represented by the formula:

wherein:

R¹⁶ is alkyl containing 1 to 25 carbon atoms; aryl containing 6 to 25 carbon atoms, alkoxy containing 1 to 25 carbon atoms, aryloxy containing 6 to 25 carbon atoms or amino of formula:

R¹⁷ is hydrogen, alkyl containing 1 to 25 carbon atoms, or acyl containing 2 to 25 carbon atoms;

R¹⁸ is alkyl containing 1 to 25 carbon atoms or acyl containing 2 to 25 carbon atoms;

R¹⁹ is hydrogen or alkyl containing 1 to 25 carbon atoms;

R²⁰ is hydrogen, carboxamido or alkyl containing 1 to 25 carbon atoms; and,

_R²¹ and _R²² are individually alkyl containing 1 to 25 carbon atoms or aryl containing 6 to 25 carbon atoms or together are the atoms selected from the carbon, hydrogen, nitrogen and oxygen atoms necessary to complete a 5 or 6 member heterocyclic group.

4. A color-forming compound according to Claim 1, which is one of the compounds:





and

5. A photographic material comprising a support having thereon, in association,

(a) photographic silver halide; and,

(b) a color-forming carboxamidonaphthalene dye precursor compound according to any one of the preceding claims.

6. A photographic material according to Claim 5 comprising a cross-oxidizing silver halide developing agent in association with the silver halide and dye precursor.

7. A photographic material according to Claim 6 wherein the cross-oxidizing developing agent is a 3-pyrazolidone.

8. A method of forming a dye image by developing a layer containing developable photographic silver halide with a cross-oxidizing developing agent in the presence of an image dye precursor which is oxidized to the corresponding image dye by an oxidation product of the developing agent, characterized in that the image dye precursor is a carboxamidonaphthalene compound comprising a benzene ring attached by an -NH- group to a naphthalene nucleus wherein:

(a) the benzene ring has a secondary or tertiary amino group in the para position relative to the -NH- group;

(b) the naphthalene nucleus has a carboxamido group in the para position relative to the -NH- group; and

(c) the benzene ring and the naphthalene ring are optionally further substituted;
the compound forming, on oxidation, a carboximide dye.

9. A method according to claim 8 wherein the image dye precursor is a compound as defined in any of claims 2 to 4.

10. A carboximide dye comprising a benzene ring attached by an -N* group to a naphthalene nucleus in quinone form wherein

(a) the benzene ring has a secondary or tertiary amino group in the para position relative to the -N= group;

(b) the naphthalene nucleus in quinone form has a carboximido group in the para position relative to the -N= group; and,

(c) the benzene ring and the naphthalene nucleus in quinone form are optionally further substituted.

11. A dye according to Claim 10 represented by the formula:

wherein each of the substituents R¹ to R⁹ and R¹² to _R¹⁵ is as defined for the formula of claim 2.

12. A dye according to Claim 11 represented by the formula:

wherein each of the substituents R¹⁶ to R²⁰ is as defined for the formula of claim 3.

13. A dye according to Claim 10 which is one of the compounds:





and